Stabilized diazonium derivative of phthalocyanine compounds



tallic tetra-amino-phthalocyanines.

Patented May 16, 1944 STABILIZED D-IAZONIUM DERIVATIVE or PHTHALOCYANINECOMPOUNDS Norman Hulton Haddock, Blackley, Manchester,

England, assignor to Imperial Chemical Industries Limited, a corporationof Great Britain No Drawing. Application August 30, 1941, Serial No.408,931. In Great Britain May 25, 1939 2 Claims. (o1. 260-141) Thisinvention deals with novel derivatives of phthalocyanine compounds,which maybe designed generically as stable derivatives of diazotisedtetra-amino-phthalocyanines. V

It is an object of this invention to provide novel compounds of thephthalocyanine series, which may be useful in dyeing textile fiber.Other and further important objects of this invention willappear as thedescription proceeds.

This application is a continuation-in-part of my-copending applicationSerial No. 335,871, filed May 1'7, 1940 (Pat. No. 2,280,072, issuedApril 21, 1942). i i

In my parent applicationI have'described a novel method for producingmetal-free and me- According to my said inventiontetra-amino-phthalocyanines are prepared by reducing the correspondingtetra-nitro-phthalocyanines by the aid of special reducing agents suchas sodium sulfide, sodium hydrogen sulfide, sodium disulfide, stannouschloride or sodium hydrosulfite.

As' typical tetra-nitro-phthalocyanines which may be economicallyemployed for this purpose, there were mentioned copper tetra-(4)-nitrophthalocyanine, copper tetra-(3) -nitro-phthalocyanine, mixturesof these; other metallic tetranitro-phthalocyanines for instance thoseof cobalt, nickel, aluminum,lead'or magnesium; and also metal-freetetranitro-phthalocyanine.

The tetra-amines thus obtained, in good yield, were described asgenerally green in color and insoluble in water. They are turned blue bythe action" of acids, for example hydrochloric acid, seemingly owing tosalt formation. When subjected to the action of nitrous acid, they arereadily diazotised, and in this form are useful as intermediates, namelydiazo components, in the preparation of coloring matters.

Moreover, the tetra-diazo compounds thus obtained may be precipitated ina form suitable for technical handling, that is in'solid state, byadding to the solutions thereof, zinc chloride, cadmium chloride orother salt suitable for the production of double salts or naphthalene orother sulphonic acids which will give sulphonic acid salts of thetetra-diazo compounds sparing- 1y enough soluble in water to beprecipitated, e. g.

naphthalene 1:5-disulphonic acid. Other tetradiazonium derivatives mayalso be obtained in the solid state, namely the alkali salts of thephthalocyanine .iso-diazotates. The latter .I have found can be made bythe usual methods employed in converting aromatic diazonium salts intothe corresponding iso-diazotates- For ex-- ample, the potassiumtetra-'(4)iso-diazotate of copper'phthalocyanine is prepared by adding asolution oi the'tetra-diazonium chloride to an excess of aqueouspotassium hydroxide at C. and then adding the mixture to a large vol--ume of concentrated aqueous potassium hydroxide at not less than aboutC.

The present application is concerned primarily with the said solidtetradiazonium derivatives.

I have found that the above stable derivatives oftetradiazo-phthalocyanines, whether of the double-salt type or of thesulfonate type or of the isodiazotate type possess valuable properties,and may be used as intermediates for the production of phthalocyanineazo dyestuffs either in substance or on the fiber.

Thus, they may be applied to cellulosic fiber from aqueous bath and thendeveloped on the fiber with various azoic coupling components, producingviolet to green and grey shades of good fastness properties, includingoutstanding faste mess to washing. Among the azoic coupling mponentssuitable for this purpose may be mentioned B-naphthol,2-hydroxy-3-naphthoic anilide, bis-acetoacet-o-tolidide,l-phenyl-B-methyl- S-pyrazolone, resorcinol, u-llaPhthOl,2:3-hydroxy-naphthoic-o-toluidide, 2 B-hydroxynaphthoic-p-anisidide andthe p-chloranilide of 2-hydroxycarbazole-B-carboxylic acid. Or thediazonium derivatives may be coupled to said azoic coupling componentsin a reaction vessel, producing the corresponding pigments in substance.

Alternatively, the stable phthalocyanine-diazonium derivatives of thisinvention may be applied to the fiber from aqueous bath, and thentreated on the fiber with reagents and under conditions adapted todecompose the diazonium groups liberating nitrogen, producing on thefiber insoluble phthalocyanine derivatives. Green to blue shades ofexcellentfastness properties may thus be obtained. The developingsubstances selected. for this purpose may be organic or inorganiccompounds, and the vast field of applicable agents may be illustrated bythe following: wa-

ter, ethyl alcohol, potassium iodide, potassium bromide, potassium ethylxanthate, sodium ethyl Xanthate, pyridine, sodium stannite, sodiumsulphite, sodium oleyl sulphate, potassium ferrocyanide, ammonia, sodiumsulphide, formic acid,

sodium thiosulphate,v benzoquinone, hydrazine sulphate, potassiumcyanate, sodium formats, sodium hypoposphite, sodium thiocyanate, sodiumcuprocyanide and alkaline formaldehyde.

The dry phthalocyanine diazonium compounds are green powders which arestable at ordinary temperature and can be stored for long periods out ofcontact with moisture. The double-salts and the iso-diazotates arereadily soluble in water; the sulphonates are sparingly so. Thesolutions in water lose nitrogen rapidly on warming with the formationof green precipitates.

The invention is illustrated but not limited by the following examples,in which the parts are by weight.

Example 1 water, are added slowly so that the temperature does notexceed 20 C. After stirring for 20 hours 100 parts of 10% sodiumsulphite solution are added. The dark green product is filtered off,washed well with water and dried.

Instead of 24 parts of crystalline .sodium sulphide, 21 parts of 27%sodium disulphide solution may be used.

The zinc chloride double salt of copper tetral) -diazoniumphthalocyaninechloride is made as follows: 12.3 parts of finely divided copper tetra-(4) -aminophthalocyanine in the form of an aqueous paste are mixed with120 parts of water and 6 parts of sodium nitrite. This mixture, cooledto 5 C., is then added to 90 parts of concentrated aqueous hydrochloricacid (sp. gr. 1.16) previously cooled to C. To the clear dark greensolution of diazo compound thus obtained there is added a solution of 25parts of zinc chloride in 50 parts of 0.5% aqueous hydrochloric acid.There is formed a dark green finely divided precipitate. This isfiltered off, washed with acetone and dried. This is a zinc double salt.It is readily soluble in cold water to give a greenish blue solution.

Example 2 10 parts of copper tetra-(4)-nitrophthalocyanine in the formof a finely milled 10% aqueous paste is stirred in an ice-bath. "34parts of 30% aqueous sodium hydrogen sulphide solution are added at sucha rate that the temperature of the mixture does not exceed 25 C. After'20 hours, the dark green suspension is diluted with 70 parts of 10%sodium sulphite solution. The product is filtered off, washed withaqueous sodium-sulphite and then with water. It may now be dried to agreen powder or conveniently the wet filtercake may be used for asubsequent chemical operation, e. g. diazotisation.

The potassium tetra-( D-iso-diazotate of copper phthalocyanineismade asfollows:

30 parts of finely divided copper tetra-(4)- amino-phthalocyanine in theform of an aqueous paste are mixed with 350 partsof water and 150 partsof concentrated aqueous hydrochloric acid (sp. gr. 1.16). To the mixtureat 5 C. is added a solution of 15 parts ofsodium nitrite in 50 parts ofwater. The temperature is maintained throughout at 5 C. or below. Thedark green diazo solution is now added to a stirred mixture at -l0 C. of1200 parts of potassium hydroxide and 800 parts of water. The greensolution so obtained is added rapidly to a mixture of 1600 parts ofpotassium hydroxide and 400 parts 'of waterpreviously heatedto 120 C.The temperature is maintained at not less than 120 C. during theaddition. The mixture is'cooled to 100 C. and the tetra-isodiazotate, insuspension, is filtered off through asbestos paper. It is pressed undervacuum till dry. The :product is a dark green powder soluble in coldwater to give a bluish green solution.

Example 3 parts of copper tetra-(4)-nitrophthalocy-anine in the form ofa finely milled aqueous paste are stirred with 200 parts of 33% aqueous200 parts of a 16% sodium hydroxide solution and themixture boiled for 5minutes after which it is filtered hot. This process is repeated untilthe product is free from tin and finally, the coppertetra-(4)-aminophthalocyanine, so obtained, is washed with waterunti1free from inorganic matter and dried. It is green in colour andbecomes blue on treatment with sulphuric acid.

Copper tetra-(4)-aminophthalocyanine is diazotised as follows. 30 partsthereof as a finely milled aqueous paste are stirred with 20 parts ofsodium nitrite and in all 500 parts of .cold water. To this mixture (atbelow 10 C.) is quickly added with stirring 500 parts of 33% aqueoushydrochloric acid. .After a few minutes stirring a clear deep greensolution of the tetradiazo compound is obtained.

The same result is obtained when the suspension of tetra-amino compoundin aqueous sodium nitrite is addedt'to the aqueous hydrochloric acid.

The copper phthalocyanine tetra-(4)-di-azonium chloride obtained aboveis converted into a stable salt with naphthalene-1:5-disulphonic acid asfollows. The solution of the copperphthalocyanine tetra-(4) -diazoniumchloride (derived from 30 parts of copper tetra-(4)-aminophthalocyanine)which is at a temperature of 5 C. is added to a solution of parts ofdisodium naphtha- .lene-lrS-disulphonate in 1200 parts of Water,previously cooled to 0 C. The precipitated sulphonic acid salt isfiltered off and washed with acetone and dried. The green product isvery sparingly soluble in water.

Instead of being caused to interact with .naphe thalene-l5-disu1phonic'acid, the copper phthalocyanine tetra-(4) -diazoniumchloride obtained above may be 'convertedinto the correspondingisodiazotate in the manner described in Exam- .ple 2.

In a similar manner cobalt :tetra-aminophthalocyanine,metal-free-tetra-aminophthalocyapended claims.

The species of theabove invention not :included in the :scope of thesubjoine'd claims are being claimed in my copending applicationsSerialNos. 443,668'and 443,669, filed May 19, 1942.

I claim:

1. A tetra-diazoniumderivative of the'phthalocyanine series, stabilized:in solid .iform :by :salt

formation with-amaromatic sulfonic acid.

2. The naphthalene-l,5edisulfonicacidsalt--.of tetra-diazonium-copperphthalocyanine.

NGRMAN HULTON .H-ADDOCK.

